<jats:title>Abstract</jats:title><jats:p>The main biochemical function of the tocopherols is believed to be the protection of polyunsaturated fatty acids (PUFA) against peroxidation. A critical question that must be asked in reference to this is whether there is a biochemical link between the tocopherol levels and the degree of unsaturation in vegetable oils, the main source of dietary PUFA and vitamin E. We used a mathematical approach in an effort to highlight some facts that might help address this question. Literature data on the relative composition of fatty acids (16:0, 16:1, 18:0, 18:1, 18:2, and 18:3) and the contents of tocopherols (α‐, β‐, δ‐, and γ‐tocopherol) in 101 oil samples, including 14 different botanical species, were analyzed by principal‐component analysis and linear regression. There was a negative correlation between α‐ and γ‐tocopherols (<jats:italic>r</jats:italic>=0.633, <jats:italic>P</jats:italic><0.05). Results also showed a positive correlation between linoleic acid (18:2) and α‐tocopherol (<jats:italic>r</jats:italic>=0.549, <jats:italic>P</jats:italic><0.05) and suggested a positive correlation between linolenic acid (18:3) and γ‐tocopherol.